Method of activating per-compounds and solid activated per-compound compositions

ABSTRACT

THE METHOD OF ACTIVATING AQUEOUS SOLUTIONS OF PERCOMPOUNDS UTILIZING AN ACTIVATOR DIACYLATED 2,5-DIKETOPIPERAZINE AND SOLID ACTIVATED COMPOSITIONS OF SOLID PERCOMPOUNDS AND AN ACTIVATOR DIACYLATED 2,5-PIPERAZINE, SAID ACTIVATOR DIACYLATED 2,5-DIKETOPIPERAZINE HAVING THE FORMULA   2,5-DI(O=),1-R1,3-R4,4-R2,6-R3-PIPERAZINE   WHEREIN R1 AND R2 ARE ACYLS OF ORGANIC CARBOXYLIC ACIDS HAVING FROM 2 TO 9 CARBON ATOMS AND R3 AND R4 ARE MEMBERS SELECTED FROM THE GROUP CONSISTING OF HYDROGEN, ALKYL HAVING FROM 1 TO 3 CARBON ATOMS, HYDROXYALKYL HAVING 1 TO 3 CARBON ATOMS, HALOALKYL HAVING 1 TO 3 CARBON ATOMS, NITROALKYL HAVING 1 TO 3 CARBON ATOMS, NITRILOALKYL HAVING 2 TO 4 CARBON ATOMS AND ALKOXYALKYL HAVING 2 TO 5 CARBON ATOMS.

United States Patent 3,775,332 METHOD OF ACTIVATING PER-COMPOUNDS AND SOLD) ACTIVATED PER-COMPOUND COMPOSITIONS Arnold Heins, Hilden, Dieter Kiihling, Monheim, and Helmut Bloching, Hilden, Germany, assignors to Henkel 8: Cie GmbH, Dusseldorf-Holthausen, Germany No Drawing. Filed Aug. 2, 1971, Ser. No. 168,374 Claims priority, application Germany, July 31, 1970, P 20 38 106.0; Oct. 21, 1970, P 20 51 554.2 Int. Cl. Clld 7/54 U.S. Cl. 252-95 22 Claims ABSTRACT OF THE DISCLOSURE The method of activating aqueous solutions of percompounds utilizing an activator diacylated 2,5-diketopiperazine and solid activated compositions of solid percompounds and an activator diacylated 2,5-piperazine, said activator diacylated 2,5-diketopiperazine having the formula wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbon atoms and R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitn'loalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms.

THE PRIOR ART Solid inorganic per-compounds, especially perborates, are known as active substances present in many oxidizing and bleaching agents, which are used for a large number of different purposes, but especially for bleaching and in some cases for the simultaneous washing of textiles. The active oxygen of the inorganic per-compounds in generally only active at temperatures above 70 C. and preferably in the range from 80 C. to 100 C. so that only textiles insensitive to temperature can be bleached by means of inorganic per-compounds. Of course, washing agents containing such inorganic per-compounds, and especially perborates, are frequently used for washing textiles sensitive to temperature, generally at temperatures from 30 C. to 50 C., that is, in a range in which the active oxygen present in these washing agents is not yet fully active. The agent is therefore not fully utilized and a part remains unused in the wash liquor.

Aqueous solutions of inorganic per-compounds, especially of hydrogen peroxide or perborates, have been used for a long time as oxidizing and bleaching agents for a larger variety of materials. However, as indicated above, for practical purposes the active oxygen released by the per-compounds does not act with sulficient speed until tempertures above 70 C., and preferably in the range from 80 C. to 100 C., are reached. Therefore, these bleaching agents cannot be used with materials which are sensitive to temperaure. When such materials have to be bleached, this has to be effected at relatively low temperatures.

It has already been proposed to add certain N-acyl compounds to the aqueous solutions of per-compounds in order to activate the latter. According to the German "Ice specification 1,162,967 compounds are to be used for this purpose which have at least two acyl groups linked to the same nitrogen atom, for example, N,N,N-triacetylmethylenediamine and N,N,N,N'-tetraacetylmethylenediamine. According to U.S. Pat. No. 3,177,148, compounds of the general formula RCONR OCR in which R and R signify C alkyl residues, and R may represent any optional organic radical which can be united with R to form an optionally substituted caprolactam-, N-acylated barbitone-, phthalimide, anthranilic-, N-acylated hydantoinor saccharine ring, serve for this purpose.

The copending commonly-assigned U.S. patent application Ser No. 141,372, filed May 7, 1971, now Pat. No. 3,715,184, describes the method of activating aqueous solution of per-compounds, utilizing as activator, acylated glycolurils of the formula in which at least two of the residues R to R represent acyl residues having 2 to 8 carbon atoms, while the other residues represent hydrogen atoms and/or alkylor arylresidues with 1 to 8 carbon atoms and/or acyl residues with 2 to 8 carbon atoms. The acyl residues present in the molecule may be the same or different; tertaacylglycolurils with the same C acyl residues, especially tetraacetylglycoluril, are preferably used.

OBJECTS OF THE INVENTION An object of the present invention is the development of materials which will activateper-compounds, particularly at temperatures below 70 C.

Another object of the present invention is the obtention of solid, powdery to granular oxidation, bleaching and washing agents which generate active oxygen at temperatures off rom 20 C. to 70 0., preferably from 30 to 60 C.

A further object of the invention is the development of the method of activating aqueous solutions of percompounds which comprises adding to said aqueous solutions of per-compounds an effective amount of diacylatcd 2,5-diketopiperazine having the formula RaCH wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbon atoms and R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitriloalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms.

A further object of the invention is the obtention of aqueous compositions of per-compounds and diacylated 2,5-diketopiperazines which are active at temperatures below 70 C. in aqueous solutions.

Another object of the present invention is the obtention of solid, powdery to granular oxidation, bleaching and washing agents comprising a content of a solid inorganic per-compound and an effective amount of diacylated 2,5- diketopiperazine activators having the formula wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbon atoms and R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitriloalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms.

These and other objects of the invention will become more apparent as the description thereof proceeds.

DESCRIPTION OF THE INVENTION The invention relates to the use of certain organic substances as activators for per-compounds when dissolved in aqueous solutions, which enable the minimum temperature needed for a practically effective bleaching and oxidation to be reduced and/or oxidation process to be accelerated, to give washing liquors with a cold bleaching activity.

The substances to be used as activators for the percompounds according to the invention are diacylated 2,5- diketopiperazines of the following formula in which R and R represent acyl residues of organic carboxylic acids with 2 to 9 carbon atoms and R and R each represent hydrogen or optionally substituted bydrocarbon residues containing 1 to 3 carbon atoms.

The activators to be used according to the invention are marked by a better activating action as compared with known activators.

The present invention also provides solid, powdery to granular oxidation, bleaching and Washing agents comprising a solid inorganic per-compound and, as an activator, the diacylated 2,5-diketopiperazines having the above formula.

Preferred as activators are diacylated 2,5-diketopiperazines having the formula wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbon atoms selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acd, halobenzoic acid, alkylbenzoic acid, nitroalkylbenzoic acid, haloalkylbenzoic acid, alkoxybenzoic acid and nitrilobenzoic acid, and R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitriloalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms.

The said compounds are therefore used as activators for H 0 or per-compounds (peroxycompounds) yielding H202 in Water.

These activators are marked by an improved activating action compared with the known activators.

Diacyl-diketopiperazines with the same R and R residues are easier to prepare than those with different acyl residues; therefore the former have greater practical importance. When the residues R and R are aliphatic, they preferably contain 2 to 4 carbon atoms, and when they represent aromatic residues, they may contain up to 9 carbon atoms. Consequently the following are preferably used as the residues R and R acetyl, propionyl, nor isobutyryl, benzoyl, toluoyl or xyloyl. Suitable substituents are C alkoxy groups, halogen atoms, and nitro or nitrile groups; chloroand/or nitrosubstituted aromatic residues which are of especially practical interest are n-chloroor mor p-nitro substituted residues. The residues R and R are preferably the same, for example, methyl or ethyl residues optionally substituted by hydroxyl groups, halogen atoms, or nitro, nitrile, methoxy or ethoxy groups. Preferred are those compounds where R and R are the same and are acyls of alkanoic acids having 1 to 4 carbon atoms, nitriloalkanoic acids having 3 to 4 carbon atoms, haloalkanoic acids having 2 to 4 carbon atoms, benzoic acid, halobenzoic acids, nitrobenzoic acids, nitrilobenzoic acids and methoxybenzoic acids; and R and R are the same and are hydrogen or alkyl having 1 to 3 carbon atoms.

Suitable acyl residues of organic carboxylic acids having from 2 to 9 carbon atoms are, for example, alkanoyls, such as acetyl, propionyl, butyryl, etc.; haloalkanoyls, such as monobromoacetyl and preferably chloroalkanoyls such as monochloroacetyl, dichloroacetyl, trichloroacetyl, etc.; nitriloacetyl, benzoyl and toluyl which may be sub stituted with nitro groups or halogen atoms such as chlorobenzoyl, nitrobenzoyl, chlorotoluyl and nitrotoluyl; methoxybenzoyls; and nitrilobenzoyls. Suitable alkyls having 1 to 3 carbon atoms are, for example, methyl, ethyl, etc.

According to the invention the diacetyl, dipropionyland dibenzoyl-diketopiperazines are of special practical importance; in addition to these, dibutyryl-, dinitrilo-, acetyl-, dimonochloroacetyl-, di-dichloroacetyl-, di-trichloroacetyl-, di-m-chlorobenzoyl-, dinitrobenzoyl-, dimethoxybenzoylor dinitrilobenzoyl-diketopiperazines or the corresponding derivatives alkylated in the 3- and/or 6-position can be used.

Of the acylated diketopiperazines to be used as activators according to the invention, the diacetyland dibenzoyl derivatives are known (see Berichten der Deutschen Chemischen Gesellschaft, 1897, 30, p. 1585 and 1921, 54, p. 2691). These compounds are obtained by acylation of the diketopiperazine with the corresponding carboxylic acid anhydrides or carboxylic acid halides.

In an analogous way the diketopiperazines alkylated in the 3- and/or 6-position can be acylated. The alkylated piperazines to be used as starting materials are obtainable according to Bulletin de la Societe Chimique de France, 1942, pp. 487-494, by condensation of the corresponding amino acids. The 3,6-dimethyl-2,S-diketo-peperazine can be acetylated according to Recueil des Travaux Chimiques des Pays-Bas, 1908, 27, p. 205.

The following, for example, are obtainable by such processes: dipropionyl, dibutyryl, dinitriloacetyl, dimonochloroacetyl, di-dichloroacetyl, di-trichloroacetyl, di-mchlorobenzoyl, di-nitrobenzoyl, dimethoxybenzoyl or dinitrilobenzoyl-diketopiperazine and the corresponding derivatives alkylated in the 3- and/or 6-position.

Dipropionyl-diketopiperazine is obtained, .for example, by the following method: A suspension of 22.8 g. (0.2 mol) of 2,5-diketopiperazine in 350 ml. (2.7 mols) of propionic anhydride is stirred for 3 hours at C. After cooling, undissolved material is filtered off and the clear filtrate is evaporated in vacuo. The crude 1,4-dipropionyl- 2,5-diketopiperazine thus obtained is already utilisable in this state as an activator for percompounds. However it can be purified by washing with water and isopropanol and then recrystallising from isopropanol, a yield of 23.5 g. (52.7% of theory) being then obtained. The melting point is 113-1145" C.

The analysis values calculated for the formula agreed satisfactorily with the values found (C calc.: 53.09%, found: 53.26%; H calc.: 6.24%, found: 5.94%; N calc.: 12.38%, found: 12.49%); the IR, NMR and mass spectra agreed with these to be expected for 1,4-dipropionyl-2,S-diketopiperazine.

For the preparation of l,4-dipropionyl-3,6-di-methyl- 2,5-diketopiperazine, a suspension of 28.4 g. (0.2 mol) of 3,6-dimethyl-2,S-diketopiperazine in 130 g. (1 mol) of propionic acid anhydride is treated with 0.5 ml. of 70% perchloric acid and the mixture is heated for 8 hours at 120 C. to 125 C. The clear solution obtained is concentrated and the crude dipropionyl-dimethyl-diketopiperazine obtained as residue is digested with petrol (B.P. 80*- lO C.), filtered by suction and the residue is again washed with petrol. The crude product is obtained in a yield of 14.8 g. (29.3% of theory). The melting point lies at 106 C. to 114 C. It can be used in this state as an activator. However, after recrystallizing from isopropanol, the pure product used for analysis melts at 113 C. to 114 C.

The analysis values calculated for the formula agreed satisfactorily with the values found (C calc.: 56.68%, found: 56.59%; H calc.: 7.13%, found: 7.23%; N calc.: 11.02, found: 11.13%).

The per-compounds to be activated can be any type of inorgnaic or organic per-compound which will release active oxygen in an aqueous solution. For economic reasons, the per-compounds preferably utilized are inorganic peroxides, inorganic per-acids, inorganic peroxyhydrates and products of the addition of hyrogen peroxide with inorganic and organic compounds.

Of the peroxides to be activated, hydrogen peroxide is of the greatest practical importance. It may be used as such, but may also be used in the form of its mostly solid peroxyhydrates or products of addition with inorganic and organic compounds. The latter include, for example, the products of addition of hydrogen peroxide to urea or melamine, and examples of the peroxyhydrates are the perborates, perortho-, perpyro-, and perpoly-phosphates, percarbonates and persilicates. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts. The activators according to the invention, however, may also be used together with true per-acids, such as for example Caros acid (peroxymonosulfuric acid, H 50 or peroxydisulfuric acid (H S O or their salts.

Each acyl residue present in the diacetylated 2,5-diketopiperazine activator is able to activate an active oxygen atom of the per-compound used. Therefore, in theory, the activator and per-compound should be used in equivalent amounts for complete activation of the active oxygen present. In practice, however, satisfactory effects are attained in many cases even with substantially smaller amounts of activator, while on the other hand, the activator may also be used in relatively large excess. It has been found that the activating effect can occur with addition of very small amounts of 0.04, preferably 0.1 acyl groups per atom of active oxygen. Excesses, however, may be utilized up to 6 acyl groups per atom of active oxygen. Preferably 0.5 to 6, more particularly 0.75 to 3, acyl groups are supplied per atom of active oxygen.

The acceleration of the bleaching and oxidizing processes is shown both at at low temperature in the range from 10 to 70 and preferably from 30 to 60 C., and at temperatures above these limits, which may go up to C. Depending upon the problem to be solved, it is possible for the technician, when using the activators ac cording to the invention, either to reduce the temperature of treatment and/ or to shorten the time of treatment, the temperature remaining the same. Finally, a low and a high temperature bleach can also be combined in one operation. In such cases it may be advantageous to add less than the theoretiical amounts of activator; then at low temperatures only a part of the active oxygen present is activated, and the remainder is available for the bleaching at elevated temperatures.

The conditions to be maintained during operation with the activators according to the invention, such as for example, the concentration of the peroxide, temperature, pH value and time of treatment, depend substantially on the substance to be oxidized and/or bleached, and in some cases on the carrier material on or in which the substance to be bleached is present. The usually aqueous oxidizing or bleaching liquids may contain 5 mg. to 500 mg., preferably 10 mg. to 250 mg. per liter of active oxygen and have a pH value from 7 to 13, preferably from 7.5 to 12, and especially from 8 to 11.

As previously stated, aqueous solutions of per-compounds and diacylated 2-5 diketopiperazine activators, optionally with other ingredients as indicated below, may be utilized. These aqueous solutions preferably contain sufiicient per-compounds to give a concentration of from 5 mg. to 500 mg., preferably 10 mg. to 250 mg. per liter of active oxygen and sufficient diacylated 2,5-diketopiperazine activators to provide from 0.04 to 6, preferably 0.75 to 3 acyl residues of the diacylated 2,5-diketopiperazine per active oxygen atom.

The activators, according to the invention, may be used wherever per-compounds, especially hydrogen peroxide or perborates, have previously been used as oxidizing and/ or bleaching agents. This applies, for example, to the bleaching of oils, fats and waxes, to cosmetic skin treatment, in disinfection or sterilization, in passivation of aluminum or other light metal surfaces, and especially in the bleaching of fibrous substances of all kinds.

The desired pH value is adjusted by addition of acid-, neutralor alkaline-reacting substances, possibly by bufier mixtures, and particularly by additives which have also been co-employed in a corresponding, formerly customary, treatment.

These frequently include the surface-active substances which serve to decrease the surface tension of the aqueous oxidizing or bleaching liquid, such as for example, soap or known synthetic detergents of anionic, non-ionic, amphoteric or cationic nature. When working in the alkaline range, alkaline substances may be added as well as inorganic or organic complex-forming compounds, especially complex-forming compounds suitable for binding the socalled hardness-producing substances in water or heavy metals which may possibly be present.

As indicated, the present invention also provides solid, powdery to granular oxidation, bleaching and washing agents comprising a solid inorganic per-compound and the activator diacylated 2,5-diketopiperazines.

The minimum temperature necessary for an effective oxidation or bleaching with solid inorganic per-compounds is reduced by the addition of these diacylated 2,5- diketopiperazines and/ or the oxidation or bleaching process is accelerated. The advantages of the presence of the activators are not, however, restricted to the activation of the per-compounds present. The activators contained in the products according to the invention are advantageous- 1y encased, so that they do not come into direct contact with the other constituents of the products, especially with the per-compounds preferably contained therein. This frequently enables the stability of such mixtures on storage to be improved.

In the oxidizing, bleaching and washing agents the combination according to the invention of solid inorganic percompounds, activator and possibly a stabilizer for the per-compound, constitutes from 10% to 100% of the total composition.

The other customary components of cold bleaching liquors include especially substances which are contained in bleaching pre-washing or complete-washing compositions, for example, neutral and/or alkaline-reacting builders, per-compounds yielding H in aqueous solution, stabilizers for per-compounds, complex-forming substances, surface-active compounds, additives for increasing or reducing the foaming power of the surface-active compounds, textile softeners, soil suspending agents, enzymes, brighteners, substances for protecting against corrosion, antimicrobial substances, perfume and dyestulfs.

The compositions with a content of from 2% to 90% by weight of the above-mentioned activators serving according to the invention for the preparation of cold bleaching liquors, especially washing liquors with a cold bleaching activity, need not necessarily contain per-compounds. Such products are suitable, for example, for use in the textile industry or in industrial laundries, where together with hydrogen peroxide or with solid per-compounds, and possibly the usual additives, they serve for the preparation of the bleaching and washing liquors. However, such products can also be used advantageously in the houshold as packed additives or in the form of tablets for joint use with activator-free bleaching washing compositions.

Such products frequently contain in addition to activators and further additives; also certain amounts of the usual neutral and preferably alkaline-reacting builders customary in washing assistants and washing compositions, so that their composition lies within the following formulation:

10% to 90%, preferably 20% to 70% by weight of the activator described above;

90% to 10%, preferably 80% to 30% by weight of neutralor preferably alkaline-reacting builders customary in washing assistants and washing composition; and

0 to 30%, preferably 1% to 20% by weight of other customary components of bleaching liquors, as for example stabilizers for per-compounds, compounds forming complexes with heavy metals, corrosion inhibitors and brighteners.

Since the action of the activators is combined with a consumption of alkali, the builders should contain sulficient amounts of strongly alkaline-reacting salts, for example alkali metal carbonates, in order to prevent the pH value of the bleaching and washing liquor from falling below the desired value.

Obviously per-compounds yielding H 0 in aqueous solution can also be incorporated in such products which are preferably intended for the textile industry or for industrial laundries. The composition of such products preferably lies within the following formulation:

5% to 90% by weight of a bleaching component comprising the activator used according to the invention and a solid per-compound yielding H 0 in water, the amount of activator constituting at least 2% by weight of the total composition and 0.05 to 2, preferably 0.1 to 1 mol of activator being present per active oxygen atom;

90% to 0, preferably 80% to 30% by weight of neutraland preferably alkaline-reacting builders;

0 to 30%, preferably 1% to 20% by weight of other usual components of bleaching liquors or of bleaching washing liquors, for example, stabilizers for per-compounds, compounds forming complexes with heavy metals, corrosion inhibitors and brighteners.

Both the special products, preferably for use in the textile industry or in industrial laundries and the steeping, pre-washing and washing compositions, preferably for use in the household, fall within this formulation.

The former usually contain more than 40% by Weight of per-compounds and activators, this amount relating to the pure activator and to the pre per-compound. Such products may of course also be used for special purposes in the home, for example as soaking or washing compositions with an increased bleaching action, which may also serve as cold washing compositions or as bleaching after-rinsing composition of the washed laundry.

The products to be used as steeping, pre-washing and washing compositions mostly contain relatively small amounts of per-compounds and activators; these are usually present therein in amounts of 3% to 40%, preferably 10% to 35%. Moreover alkaline-reacting noncomplex-forming builders, complex-forming builders, and often surface-active compounds are present in such compositions as further important constituents.

Products which contain the combination of activator and per-compound used according to the invention, as well as possibly other customary constituents of bleaching and washing liquors, can also be used as bleaching soaking compositions, especially when the washing remains for a relatively long time in the solutions of the soaking agent. Such soaking agents have the following composition:

3% to 40% by weight, preferably 10% to 35% by weight of activators and per-compounds according to the invention;

0 to 5% by weight of surface-active compounds;

97% to 55% by weight, preferably to 60% by weight of preferably alkaline-reacting builders, and possibly other customary components of bleaching baths or bleaching washing liquors, for example stabilizers for per-compounds, substances forming complexes with heavy metals, corrosion inhibitors and brighteners.

Moreover, such soaking compositions may contain the washing agent components mostly used in relatively small quantities, for example, antimicrobial substances, soil suspending agents, brighteners, enzymes, perfume and dyestuffs.

A preferred field of application of the invention is the group of bleaching pre-washing and washing com positions, the composition of which generally lies within the following formulation:

(a) 5% to 40%, preferably 7% to 30% by weight of a surface-active component, containing at least one anionic and/or non-ionic surface-active compound, especially of the type of the sulfonates, sulfates, soaps and/or non-ionics, and also possibly one or more of the following substances:

0 to 10%, preferably 0.5% to 8% by Weight of foam stabilizers;

0 to 10%, preferably 0.5% to 8% by weight of nonsurface-active foam inhibitors;

(b) 10% to 92%, preferably 30% to 70% by weight of complex-forming and/ or non-complex-forming builders, at least a part of these builders having an alkaline reaction and the amount of the alkalineto neutralreacting builders preferably constituting 0.5 to 7 times, and especially 1 to 5 times, that of the total combination of surface-active compounds present;

(0) 3% to 40%, preferably 10% to 35% by weight of per-compounds yielding H 0 in aqueous solution and also activators for these according to the above definition;

(d) 0 to 20%, preferably 2% to 15% by weight of other washing composition components, for example, textile softeners, corrosion inhibtors, antimicrobial substances, soil suspending agents, brighteners, enzymes, perfume, dyestuffs and water.

This general formulation also includes bleaching fine washing compositions to be used at temperatures up to 70, the content of surface-active compounds of which lies mostly in the range from 8% to 40%, preferably from 12% to 40% by weight; provided these fine washing compositions are not intended for use in washing machines, especially drum washing machines, they need not contain foam inhibitors.

The washing compositions intended for use in washing machines, preferably in drum washing machines, in which the surface-active component is usually 7% to 30% by weight, are of particular practical importance; these mostly contain at least one of the following two types of surface-active compounds in the amounts given.

15% to 99%, preferably 35% to 90% by weight of sulfonates and/ or sulfates with preferably 8 to 18 carbon atoms in the hydrophobic residue;

10% to 60%, preferably 10% to 50% by weight of non-ionics, and optionally one or more of the following substances:

% to 70%, preferably to 60% by weight of soap;

0 to 10%, preferably 0.5% to 8% by weight of foam stabilizers;

0 to 10%, preferably 0.5% to 8% by weight of nonsurface-active foam inhibitors;

in which case, however, the foaming power of the surface-active component is reduced either by the simultaneous presence of different surface-active compounds which reduce the foaming power and/or foam-inhibiting soap and/or non-surface-active foam inhibitors.

The products according to the invention can be prepared by all the usual processes for the preparation of oxidizing, bleaching, washing assistant and washing compositions. Thus, for example, the separate components may be admixed in a dry, pulverulent or granular state. These mixtures can be granulated or agglomerated by known processes, by spraying them while moving with water or with aqueous solutions containing substances therein. This process is advisable particularly when anhydrous salts are present in the mixtures which crystallize with binding water.

In all these processes it is advisable to avoid a direct contact of the activators and the per-compounds in the presence of water, since the activating action then starts and a part of the activators and of the active oxygen is used up and lost.

This applies especially to the hot drying process usual in the preparation of washing assistants and washing compositions. Usually only those components are incorporated in the aqueous hot-dried batch which are unchanged by water and/ or heat, and then the other components, especially the activators, the per-compounds and possibly other components to be separately incorporated for this or other reasons, as for example enzymes, are mixed with the powder so obtained.

The particles of the diacylated 2,5-diketopiperazine activators incorporated in the oxidizing, bleaching or washing agent, may also be coated with Water-soluble high molecular weight organic substances or water-insoluble high molecular weight organic substances preferably capable of swelling in water. Suitable covering substances are, for example, gelatine, methyl cellulose, hydroxyethyl cellulose, ethyl cellulose and carboxymethyl cellulose. Solid water-soluble polyglycol ethers, including different types of solid, non-ionic surface-active substances, such as, for example, the later described polyethylene glycolpolypropylene glycol-mixed ethers, are also utilizable for this purpose.

The products according to the invention may be used in a large variety of fields as oxidizing and bleaching agents. A preferred field is in the bleaching and bleachingwashing of fibers of natural or synthetic origin. Besides the textiles of cotton, regenerated cellulose or linens to be treated chiefly at temperatures of from 70 C. to 100 C., with a concentration of usually from 1 gm. per liter to 10 gm. per liter, preferable from 2 gm. per liter to 7.5 gm. per liter of bleaching and washing agent in aqueous solution, the so-called easy-care" textiles especially can be washed and/or bleached with the agents according to the invention. Among the easy-care textiles are those consisting of cotton with a high finish or synthetic fibers,

such as, for example, of polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers, or containing at least 30% of these. Correspondingly treated synthetic fiber-cotton blended fabrics are especiall to be mentioned here as easy-care textiles, sometime also called non-iron.

Suitable temperatures for bleaching or washing these easy-care textiles are from 20 C. to 70 C., preferably from 30 C. to 60 C. Also the above-named textiles, usually bleached between 70 C. to C., may, with the use of products of the invention, be bleached at lower temperatures whereby also here a combination of lowtemperature bleaching is possible, particularly if the activator is used in a deficient amount, so that after consumption of the activator still sufficient amounts of active oxygen are available to be activated thermally. The high degree of whiteness obtainable according to the invention also at these temperatures is particularly advantageous in connection with simultaneous or subsequent treatment of the textiles with optical brighteners.

The following is a summary of other constituents which may be present in the compositions according to the invention for the production of cold bleaching liquors, especially in the washing assistant and washing compositions according to the invention, for example per-compounds yielding H 0 in water, builder substances, surface-active compounds, soil suspending agents, brighteners and enzymes.

Of the solid inorganic per-compounds, the compounds having a neutral-to-alkaline reaction in aqueous solution, especially the perborates, are of particular practical interest.

Among the various perborates, sodium perborate tetrahydrate (NaBO -H O -3H O) is of great practical importance. Dehydrated perborates, i.e., up to the approximate composition NaBO -H O may also be used partly or wholly in its place. Finally, borates NaBO -H O containing active oxygen, in which the proportions Na O:B O is less than 0.5 :1 and is preferably in the range from 0.4 to 0.15:1, and in which the proportions H O :Na is in the range from 05-41, are also useful. These products are described in German Pat. No. 901,287 and in US. Pat. No. 2,491,789.

The perborates may be wholly or partly replaced by other inorganic per-compounds, especially by peroxyhydrates, as for example, the peroxyhydrates of ortho-, pyroor polyphosphates, especially tripolyphosphate, and also the carbonates. These peroxyhydrates are preferably soluble in water and are ordinarily utilized in the form of their alkali metal salts, such as their sodium salts.

The oxidizing, bleaching and washing agents according to the invention may contain the usual water-insoluble or water-soluble stabilizers for per-compounds in amounts of from 0.25% to 10%, preferably from 2% to 7% by weight.

The various magnesium silicates are suitable as waterinsoluble stabilizers for per-compounds. These are usually precipitated products which are formed on purifying aqueous solutions of alkali metal silicates with solutions of magnesium salts. The ratio MgOzSiO may lie within the range of 4:1 to 1:4, preferably from 2:1 to 1:2. A product with a ratio MgOzSiO of 1:1 is chiefly used. These magnesium silicates may be replaced by the corresponding silicates of other alkaline earth metals, cadmium or tin. Water-containing oxides of tin are also useful as stabilizers. These stabilizers are mostly present in quantities of from 2% to 7% of the weight of the whole preparation.

The water-insoluble stabilizers may be wholly or partly replaced by water-soluble stabilizers. For this purpose the organic complex-forming compounds described hereinafter are suitable, and the amount used may be from 0.25% to 5%, preferably from 0.5% to 2.5%, of the weight of the whole preparation, depending upon the strength of the complex formed.

Suitable builders are weakly acid, neutral and alkaline reacting inorganic or organic salts, especially inorganic or organic complex-foaming substances.

Useful, weakly acid, neutral or alkaline reacting salts according to the invention are, for example, the alkali metal bicarbonates, carbonates, borates or silicates, mono-, dior tri-alkali metal orthophosphates, dior tetraalkali metal pyrophosphates, alkali metal metaphosphates known as complex-forming substances, alkali metal sulfates and the alkali metal salts of organic, non-surfaceactive sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1 to 8 carbon atoms. These include, for example, water-soluble salts of benzenetolueneor xylene-sulfonic acid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid or salts of sulfodicarboxylic acids and the salts of acetic acid, lactic acid, citric acid and tartaric acid.

Further, the water-soluble salts of higher molecular weight polycarboxylic acids are utilizable as builders, especially polymerizates of maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, methylenemalonic acid and citraconic acid. Co-polymerizates of these acids with one another or with other polymerizable substances, as for example, with ethylene, propylene, acrylic acid, methacrylic acid, crotonic acid, 3-butenecarboxylic acid, 3methyl-3butenecarboxylic acid and with vinyl methyl ether, vinyl acetate, isobutylene, acrylamide and styrene, are utilizable.

Suitable complex-forming builders are also the weakly acid reacting metaphosphates and the alkaline reacting polyphosphates, especially tripolyphosphate, in the form of their alkali metal salts. They may be wholly or partly replaced by organic complex forming substances.

The organic complex-forming substances include, for example, nitrilotriacetic acid, ethylenediaminetetraacetic acid, N-hydroxyethyl-ethylenediaminettiacetic acid, polyalkylene-polyamine-N-polycarboxylic acids and other known organic complex-forming substances, while combinations of different complex-forming substances may also be used. Diand poly-phosphonic acids of the following constitutions also belong to the other known complex-forming substances:

in which R represents alkyl and R alkylene radicals with 1 to 8, preferably 1 to 4 carbon atoms, X and Y represent hydrogen or alkyl radicals with l to 4 carbon atoms and Z represents OH, NH or NXR. For a practical application above all the following compounds are considered: methylenediphosphonic acid, l-hydroxyethane- 1,1-diphosphonic acid, l-aminoethane-l,l-diphosphonic acid, amino-tri-(methylenephosphonic acid), methylaminoor ethylamino-di-(methylenephosphonic acid) as well as ethylenediamine-tetra-(methylenephosphonic acid). All these complexing compounds may be present as free acids or preferably as the alkali metal salts.

Further, soil suspending agents or greying inhibitors may be contained in the preparations according to the invention, which hold the dirt loosened from the fiber suspended in the bath and thus prevent greying. Watersoluble colloids of mostly organic nature are suitable for this purpose, for example, the Water-soluble salts of polymeric carboxylic acids, glue, gelatine, salts of ethercarboxylic acids or ether-sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acid groups are also suitable for this purpose. Furthermore, soluble starch preparations and starch products other than those mentioned above can be used, for example, degraded starch, and aldehyde starches. Polyvinylpyrrolidone is also useful.

The components of the washing compositions and washing assistants according to the invention and especially the builders, are usually selected so that the preparations have a neutral to distinctly alkaline reaction, so that the pH value of a 1% solution of the preparation usually lies in the region from 7 to 12. Fine washing compositions have mostly neutral to weakly alkaline reactions (pH value=7 to 9.5), while steeping, pro-washing and boiling washing compositions are adjusted so that they are more strongly alkaline (pH value=9.5 to 11, preferably 10 to 11). It was previously recommended to incorporate strongly alkaline-reacting salts, as for example alkali metal carbonates, in order to bind completely the acid formed during the action of the activators or to buffer it to such an extent that the pH value is not lowered below the desired value.

The anionic, amphoteric or non-ionic tensides contain in the molecule at least one hydrophobic residue mostly containing 8 to 26, preferably 10 to 12 and especially 10 to 18, carbon atoms and at least one anionic, non-ionic or amphoteric water-solubilizing group. The preferably saturated hydrophobic residue is mostly aliphatic, but possibly also alicyclic in nature. It may be combined directly with the water-solubilizing group or through intermediate members. Suitable intermediate members are, for example, benzene rings, carboxylic acid ester or carboxylic acid amide groups, residues of polyhydric alcohols linked in ether or ester-like form, such as, for example, those of ethylene glycol, propylene glycol, glycerine or corresponding polyether residues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residue with 10 to 18, preferably 12 to 18, carbon atoms but deviations from the preferred range of carbon atoms are possible, depending on the nature of the surface-active compound in question.

Soaps from natural or synthetic fatty acids, possibly also from resin or naphthenic acids, are utilizable as anionic detergent substances, especially when these acids have iodine values of not more than 30, and preferably of less than 10.

Of the synthetic anionic surface-active compounds, the sulfonates and sulfates possess special practical importance.

The sulfonates include, for example, the alkylaryl sulfonates, especially alkylbenzene sulfonates, which are obtained from preferably straightchain aliphatic hydrocarbons having 9 to 15, especially 10 to 14 carbon atoms, by chlorinating and alkyating benzene or from corresponding terminal or non-terminal olefins by alkylation of benzene and sulfonation of the alkylbenzenes obtained. Further, aliphatic sulfonates are of interest, such as are obtainable, for example, from preferably saturated hydrocarbons containing 8 to 18 and preferably 12 to 18 carbon atoms in the molecule by sulfochlorination with sulfur dioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen, and conversion of the products thereby obtained into the sulfonates. As aliphatic sulfonates, mixtures containing alkene sulfonates, hydroxyalkane sulfonates and disulfonates are useful, which are obtained from terminal or nonterminal C and preferably C1248 olefins by sulfonation with sulfur trioxide and acid or alkaline hydrolysis of the sulfonation products. In the aliphatic sulfonates thus prepared, the sulfonate group is frequently found attached to a secondary carbon atom; however, sulfonates with a terminal sulfonate group obtained by reaction of terminal olefins with bisulfite can also be used.

Furthermore, salts, preferably dialkyli metal salts of a-sulfo-fatty acids, and salts of esters of these acids with monoor poly-hydric alcohols containing 1 to 4, and preferably 1 to 2 carbon atoms belong to the sulfonates to be used according to the invention.

Further useful sulfonates are salts of fatty acid esters of hydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the salts of the fatty alcohol esters of lower aliphatic or aromatic sulfomonoor di-carboxylic acids containing 1 to 8 carbon atoms, alkylglycerylether sulfonates and the salts of the amide-like condensation products of fatty acids or sulfonic acids with aminoethanesulfonic acid.

As tensides of the sulfate type are fatty alcohol sulfates, especially those prepared from coconut fat alcohols, tallow fat alcohols or oleyl alcohol. Useful sulfonation products of the sulfate type are also obtainable from terminal or non-terminal C olefins. Sulfated fatty acid alkylolamides or fatty acid monoglycerides, and sulfated alkoxylation products of alkylphenols (C alkyl), fatty alcohols, fatty acid amides or fatty acid alkylolamides, which may contain in the molecule 0.5 to 20, preferably 1 to 8 and especially 2 to 4 ethylene and/or propylene glycol residues, also belong to this group of surface-active compounds.

Suitable anionic surface-active compounds of the carboxylate type are the fatty acid esters or fatty alcohol ethers of hydroxycarboxylic acids, and the amide-like condensation products of fatty acids or sulfonic acids with aminocarboxylic acids, for example, with glycocoll, sarcosin or protein hydrolysates.

The non-ionic surface-active compounds, here called non-ionics, for the sake of simplicity, include products which owe their solubility in water to the presence of polyether chains, amineoxide, sulfoxide or phosphineoxide groups, alkylolamide groups and very generally, to an accumulation of hydroxyl groups.

The products obtainable by addition of ethylene oxide and/ or glycide to fatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid and sulfonic acid amides are of special practical interest. These non-ionics may contain per molecule 4 to 100, preferably 6 to 40 and especially 8 to ether residues, particularly ethylene glycol ether residues. Moreover, propylene or butylene glycol ether residues or polyether chains may be present in or at the ends of these polyether residues.

Further, products known by the trade name of Pluronics or Tetronics belong to the non-ionics. They are obtained from water-insoluble polypropylene glycols or from water-insoluble propoxylated lower aliphatic alcohols containing 1 to '8, preferably 3 to 6 carbon atoms and/or from water-insoluble propoxylated alkylenediamines. These water-insoluble (i.e. hydrophobic) propylene oxide derivatives are converted into the said non-ionics by ethoxylation until they become soluble in water. Finally, the reaction products of the above-mentioned aliphatic alcohols with propylene oxide known as Ucon- Fluid some of which are still Water-soluble, are useful as non-ionics.

The non-ionics also include fatty acid or sulfonic acid alkylolamides which are derived, for example, from monoor di-ethanolamine, dihydroxypropylamine or other polyhydroxyalkylamines, for example the glycamines. They can be replaced by amides from higher primary or secondary alkylamines and polyhydroxycarboxylic acids.

The surface-active amineoxides include, for example, the products derived from higher tertiary amines having a hydrophobic alkyl residue and two shorter alkyl and/or alkylol residues containing up to 4 carbon atoms, each.

Amphoteric surface-active compounds contain in the molecule both acid and basic hydrophilic groups. Carboxyl, sulfonic acid, sulfuric acid half ester, phosphonic acid and phosphoric acid partial ester groups are the acid groups. Basic groups include primary, secondary, tertiary and quaternary ammonium groups. Amphoteric compounds with quaternary ammonium groups belong to the betaine type.

Carboxy, sulfate and sulfonate betaines have particular practical interest on account of their good compatibility with other surface-active compounds. Suitable sulfobetaines are obtained, for example, by reacting tertiary amines containing at least one hydrophobic alkyl residue with sultones, for example propaneor butane-sultone. Corresponding carboxybetaines are obtained by reacting the said tertiary amines with chloracetic acid, or its salts or with'chloracetic acid esters and splitting the ester linkage.

The foaming power of the surface-active compounds can be increased or reduced by combination of suitable types of surface-active compounds, just as it can be changed by additions of non-surface-active organic substances.

Suitable foam stabilizers, above all in the case of surface-active compounds of the sulfonate or sulfate type, are surface-active carboxy or sulfo-betaines and also the above-mentioned non-ionics of the alkylolamide type. Moreover, fatty alcohols or higher terminal diols can be utilized for this purpose.

Products with a reduced foaming power are primarily intended for use in washing and dishwashing machines, where sometimes a limited repression of foam is suflicient while in other cases a stronger foam repression may be desired. Products which foam in the middle range of temperature up to about 65 C., but at higher temperatures (70 to C.) develop less and less foam are of special practical importance.

A reduced foaming power is frequently obtained with combinations of different types of surface-active compounds, especially with combinations of synthetic anionic surface-active compounds, particularly of (l) sulfates and/or sulfonates or of (2) non-ionics on the one hand and (3) soaps on the other hand. With combinations of the components (1) and (2) or (1), (2) and (3), the foaming power can be aifected by the particular soap used. The inhibition of foam is smaller with soaps from preferably saturated fatty acids with 12 to 18 carbon atoms, while a greater inhibition of foaming, particularly in the higher temperature range, is obtained by soaps from saturated fatty acid mixtures having 20 to 26, preferably 2,0 to 22 carbon atoms, used in an amount of from 5 to 10% by weight of the total soap fraction present in the combination of surface-active compounds.

The foaming power of the surface-active compounds can also be reduced, by the addition of known, non-surface-active foam inhibitors. These include optionally chlorine-containing N-alkylated aminotriazines, which are obtained by reacting 1 mol of cyanuric chloride with 2 to 3 mols of a monoand/or di-alkylamine having 6 to 20, preferably 8 to 18 carbon atoms in the alkyl residue. Aminotriazine or melamine derivatives which contain propylene glycol or butylene glycol ether chains, in an amount of 10 to 100 of such glycol residues per molecule, have a similar action. Such compounds are obtained, for example, by addition of corresponding amounts of propylene and/or butylene oxide to aminotriazines, especially to melamine. The reaction products from 1 mol of melamine with at least 20 mol of propylene oxide or at least 10 mol of butylene oxide are preferred. Products which are obtained by addition of 5 to 10 mol of propylene oxide to 1 mol of melamine and further addition of 10 to 50 mol of butylene oxide to this propylene oxide derivative have proved particularly effective.

Other non-surface-active water-insoluble organic compounds, such as paraflins or halogenated parafiins with melting points below 100 C., aliphatic C to C ketones and aliphatic carboxylic acid esters, which contain at least l8 carbon atoms in the acid or alcohol residue, possibly also in both of these two residues (for example triglycerides or fatty acid-fatty alcohol esters), can be used as foam inhibitors, particularly in combinations of anionic synthetic surface-active compounds and soaps.

The non-surface-active foam inhibitors are frequently only completely effective at temperatures at which they are present in the liquid state, so that the foaming behaviour of the products can be controlled by choice of 15 suitable foam inhibitors in a similar way to that by the choice of soaps from fatty acids of suitable chain lengths.

When foam stabilizers are combined with foam inhibitors dependent upon temperature, good foaming products are obtained at lower temperatures which, as the temperature approaches the boiling temperature, foam less and less.

Suitable weakly-foaming non-ionics, which can be used both alone and in combination with anionic, amphoteric and non-ionic surface-active compounds and which reduce the foaming power of more strongly foaming surfaceactive compounds, are products of addition of propylene oxide to the above-described surface-active polyethylene glycol ethers as well as the also above-described Pluronic, Tetronic and Ucon-Fluid types.

The brighteners used are mostly, although not exclusively, derivatives of diaminostilbenesulfonic acid, diarylpyrazolines and aminocoumarins.

Examples of brighteners from the class of diaminostilbenesulfonic acid derivatives are compounds of Formula I:

In the formula R and R may represent halogen atoms, alkoxy groups, the amino group or residues of aliphatic, aromatic or heterocyclic, primary or secondary amines, and residues of aminosulfonic acids, the aliphatic residues present in the above groups preferably containing 1 to 4 and especially 2 to 4 carbon atoms, while the heterocyclic ring systems are mostly 5- or 6-membered rings. The residue of aniline, anthranilic acid or anilinesulfonic acid are preferred as the aromatic amines.

Brighteners derived from diaminostilbenesulfonic acid are mostly used as cotton brighteners. The following products derived from the Formula I are at present on the market, in which R may represent residue NH-C H and R may represent the following residues:

(II) R5 R5 Ri Rs Ar -N N r y (III) CH:-CHI

In the Formula H, R and R represent hydrogen atoms, alkyl or aryl residues possibly substituted by carboxyl, carbonamide or ester groups, R, and R represent hydrogen or short-chain alkyl residues, Ar and Ar; represent aryl residues such as phenyl, diphenyl, or naphthyl, which may carry further substituents, such as hydroxy,

alkoxy, hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, carboxylic acid ester, sulfonic acid, sulfonamide and sulfonic acid groups or halogen atoms. Brighteners of this type at present available on the market are derived from the Formula HI, in which the residue R may represent the groups C1, SO NH S0 --CH=CH and COO-CH CH -0-CH while the residue R represents a chlorine atom in all cases. 9-cyanoanthracene is also now on the market as a polyamide brightener.

Furthermore, aliphatic or aromatic substituted aminocoumarins belong to the polyamide brighteners, for example, 4-methyl-7-dimethylaminoor 4-methyl-7-diethylaminocoumarin. In addition, the compounds l-(benzimidazolyl 2) 2- (N-hydroxyethyl-benzimidazolyl-2')- ethylene and l-N-ethyl-3-phenyl-7-diethylamino-carbostyril are useful as polyamide brighteners. The compounds 2,5-di-(benzoxazolyl-2')-thiophene and 1,2-di-(5-methylbenzoxazolyl-Z')-ethylene are suitable as brighteners for polyester and polyamide fibers.

When the brighteners are present together with other components of the products according to the invention as an aqueous solution or paste and are converted into the solid state by hot drying, it is advisable, in order to stabilize the brightener, to incorporate organic complexforming compounds in amounts of at least 0.1%, preferably 0.2% to 1% by weight of the solid products.

The enzymes to be used are mostly a mixture of different enzymic substances. They are called proteases, amylases, carbohydrases, esterases, lipases, oxidoreductases, catalases, peroxidases, ureases, isomerases, lyases, transferases, desmolases or nucleases, depending upon their action. The enzymic substances obtained from strains of bacteria or fungi such as Bacillus subtilz's and Streptomyces grz'seus are of particular interest, especially proteases or amylases. Preparations obtained from Bacillus subtilis have the advantage compared with others that they are relatively stable towards alkali, percompounds and anionic detergent substances and are still active at temperatures up to 70 C.

Enzyme preparations are usually marketed by the manufacturers as aqueous solutions of the active substances or with the addition of diluents, as powders. Suitable diluents are sodium sulfate, sodium chloride, alkali metal ortho-, pyroor polyphosphates, especially tripolyphosphate. Frequently moist enzyme preparations are mixed with calcined salts, which then bind water of crystallization present and the enzymic substance, possibly with agglomeration of the particles to larger particles.

When the enzymic substances are present as dry powders, liquid, paste-like and possibly also solid, nonionic, preferably surface-active, organic compounds. especially the above-described non-ionics, can be used at the usual room temperatures to bind the enzymes to the powders of the washing compositions or washing assistants. For this purpose a mixture of the respective product and the enzymic substance is preferably sprayed with the above-mentioned non-ionic substances, or the enzyme preparations is dispersed in the said non-ionic substance and this dispersion is united with the other constituents of the product. When these other constituents are solids, the dispersion of the enzymic substances in the non-ionic component can also be sprayed on the other solid constituents.

The enzymes, or combinations of enzymes with ditferent actions, are generally used in quantities such that the finished products have protease activities of 50 to 5000, preferably to 2500 LVE/g. and/or amylases activities of 20 to 5000, preferably 50 to 2000 SKBE/ g. and/or lipase activities of 2 to 1000, preferably 5 to 500 113/ g.

These data on enzyme activities result from the activities of those enzyme preparations which at the present time seem to be suitable from the economic standpoint for use in the washing composition field. From the chemical-technical standpoint the enzyme activities of the preparations can be increased as desired, so that the activities in the case of protcases and amylases may be raised, for example, up to five times, and in the case of lipases, for example, up to ten times, the highest values given above. If, therefore, in the future preparations with such high activities should be available which also economically appear appropriate for the use in the application fields, named at the beginning, products with respective higher enzyme activities can be prepared.

With reference to the determination of the enzyme activities, the following literature references are given:

Determination of the activity of proteases according to Lohlein-Volhard: A. Kunzel, Chemical Tanning Pocketbook, 6th ed., Dresden and Leipzig, 1955;

Determination of the activity of amylases: I. Wohlgemuth, Biochemische Zeitschrift, vol. 9 (1908), pp. 1-9; R. M. Sandstedt et al., Cereal Chemistry, vol. 16 (1939), pp. 712-723;

Determination of the activity of lipases: R. Willstatter et al., Hoppe-Seylers Zeitschrift fiir Physiologiche Chemie, vol. 125 (1923), pp. 110-117; R. Boissonas, Helvetica Chimica Acta, vol. 31 (1948), pp. 1571- 1576.

The following examples illustrate the practice of the invention without being limitative in any respect.

EXAMPLES 1, 2 AND 3 The usefulness of the activators according to the invention was demonstrated by the following examples:

Solutions which contained 0.615 gm. of

NaBO H20 (4 mmols) and 2.5 gm. of Na P O -lH O per liter, after addition of 4 mmols of activator, were heated to 45 and 60 respectively and maintained at the said temperature with stirring during the whole experiment. At certain intervals of time, 100 ml. samples were removed by pipette, immediately added to a mixture of 250 gm. of ice and 15 ml. of glacial acetic acid, and then, after addition of about 0.35 gm. of potassium iodide, were titrated with 0.1 N so dium thiosulfate solution using starch as an indicator.

Under the experimental conditions indicated, 8.0 ml. of thiosulfate solution were consumed with a 100% activation of the peroxy-compound used. The thiosulfate consumed and the percentage amount of activated peroxycompound are given in the Tables I, II and IH.

EXAMPLE 1 TABLE I.ACTIVATION OF PERBORATE WITH 1,4-DIACE- TYL-2,5-DIKETOPIPERAZIN E Activation attained at- Sample after :t M1. 0.1 N Percent 0 M1. 0.1 N Percent 0 minutes NazSzOa activated N82320: activated See footnote 1 at end of Table III.

EXAMPLE 2 TABLE II.-ACTIVATION OF PERBORATE WITH 1,4-DI- PROPIONYL-2,5-DIKETOPIPERAZINE 18 EXAMPLE 3 TABLE IH.-ACTIVATION OF PERBORATE WITH 1,4-DI ACETYL-3,6-DIMETHYL2,5-DIKETO PIPE RAZINE Activation attained at-- Sample after 1". M1. 0.1 N Percent 0 M1. 0.1 N Percent 0 minutes N32520:; activated NaaSnOs activated Content of active oxygen of e test solutions before addition of the activator.

As may be seen, on use of the diacetylor dipropionyldiketopiperazine the maximum degree of activation is already reached after a period of one minute, which in practice, is maintained over a certain length of time, depending on the temperature chosen. The subsequent falling off of the values is due to the spontaneous decomposition of the first formed peracetic acid. In the case of diacetyl-dimethyl-diketopiperazine, the amount of activated oxygen slowly rises in the course of the experiment. In this case, however, the amount of active oxygen still present after 60 minutes at 60 C. is greater than in the case of diacetyl-diketopiperazine. The products, therefore, ditfer in the period of activation, and it is possible to choose an activator the action of which is optimally adapted to the bleaching or oxidizing process in question.

These solutions can be used as oxidizing and bleaching liquids over a very wide range, and they have also good antimicrobial properties.

If only 0.5 mol of activator is used per gram-atom of active oxygen in the described experiments, a smaller activation is indeed obtained, but for many technical purposes it is completely satisfactory.

EXAMPLE 4 Solutions which contained 630 mg./l. of a commercial sodium perborate tetrahydrate with about 94% by weight active oxygen (4 mg.-atom/l. active oxygen) and 2.5 gm./l. Na P O -10H O, were, after addition of 792.8 mg./l. diacetyldiketopiperazine (4 mmols/L, corresponding to 2 acetyl radicals per active oxygen), kept at 20 C. under constant stirring. In definite time periods ml. were pipetted oif, immediately put on a mixture of 250 gm. ice and 15 ml. glacial acetic acid and subsequently, after addition of about 0.35 gm. potassium iodide, titrated with 0.1 N sodium thiosulfate solution and starch as indicator. The pH of this solution, measured immediately after addition of the diacetyl-diketopiperazine, was 10.15; in two parallel experiments solutions were processed whose pH values were adjusted by the addition of borate and hydrochloric acid, or of boric acid, potassium chloride and sodium hydroxide to 8.15 and 9.93.

Under the experimental conditions indicated for a 100% activation of the peroxy-compound used about 8.0 ml. thiosulfate solution are consumed. In Table IV the percent activation is calculated from the theoretical maximum consumption and the actual use of thiosulfate solution.

TABLE IV Percent oxygen activated at 20 C. activator: diacetyl diketo- From the foregoing and Table I, it can be seen that the extent of activation is dependent upon the pH, the temperature and the amount of the activator used.

The following examples describe compositions of some preparations according to the invention. The salt-like components contained therein, salt-like surface-active compounds, other organic salts and inorganic salt, are present as sodium salts, provided it is not expressly indicated otherwise. The meaning of the terms and abbreviations used is as follows:

ABS is the salt of an alkylbenzenesulfonic acid with 10 to 15, preferably 11 to 13 carbon atoms in the alkyl chain, obtained by condensation of straight-chain olefins with benzene and sulfonation of the alkylbenzene so formed.

Alkanesulfonate is a sulfonate obtained from paraflins with 12 to 16 carbon atoms by the sulfoxidation method.

HPK-sulfonate and HT-sulfonate are the a-sulfonates obtained from the methyl esters of a hardened palm kernel and a hardened tallow fatty acid respectively by sulfonation with S Olefinsulfonate is a sulfonate obtained from mixtures of olefins having 12 to 18 carbon atoms by sulfonation with 80;, and hydrolysis of the sulfonation product with caustic liquor, and consists substantially of alkenesulfoamounts of disulfonates. Products can be utilized which have been prepared from aor non-terminal olefins.

KA-sulfate and TA-sulfate are the salts of sulfated, substantially saturated fatty alcohols, prepared respectively by reduction of coconut fatty acid and tallow fatty acid.

KA-EO-sulfate is the sulfated product of the addition of 2 mols of ethylene oxide to 1 mol of fatty alcohol.

OA-i-IOEO, KA+20EO and Fs-amide+8EO are the products of addition of ethylene oxide (E0) to technical oleyl alcohol (0A), coconut alcohol (KA) and coconut fatty acid amide respectively, while the numbers relate to the molar amounts of ethylene oxide added on to 1 mol of starting compound.

KA+9EO+12PO is a non-ionic product obtained by reaction of 1 mol of KA+9EO with 12 mols of propylene oxide.

Carboxybetaine and sulfobetaine are the respective betaines obtained by reaction of 1 mol of coconut alkyldimethylamine with 1 mol of chloroacetic acid and with 1 mol of propanesultone.

' CMC is the sodium salt of carboxymethylcellulose.

NTA n DIET-P, HE-EDP, and ATMP are the sodium salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, hydroxyethanediphosphonic acid and aminotrimethylenephosphonic acid repectively.

Perborate (mono) and perborate (tetra) are a perborate monohydrate and perborate tetrahydrate of the approximate composition NaBO -H O and NaBO H20 31 120.

Activator is 1,4diacetyl-Z,S-diketopiperazine.

The composition of the fatty acid mixtures, from which the soaps B, C and D were prepared, is seen from the following Table V. Table V also contains the composition of the fatty acid mixture of a soap G. If the soaps B, C and D mentioned in the examples are replaced by the same amount of soap G, the foaming power of this washing composition will be distinctly greater than that of the corresponding Washing composition with soap C, but somewhat less than that of the corresponding Washing composition with soap B.

TABLE V.-COMPOSITION OF THE FATTY ACID MIXTURES CORRESPONDING TO THE SOAPS Percent (w t.) of fatty acid component A mixture of about 45% of a di-(alkylamino)-monochlorotriazine and about 55% of a N,N,N"-trialkylmelamine was used as foam inhibitor. In all these triazine derivatives the alkyl residues were present as a mixture of homologs with 8 to 18 carbon atoms. The monochlorotriazine derivative or the trialkylmelamine could also be used with a similar result. If the products described contained synthetic sulfates or sulfonates together with a soap, the other non-surface-active foam inhibitors mentioned in the specification could be used, as for example, parafiin oil or paraffin. In the production of the preparations, the foam inhibitor used, dissolved in a suitable organic solvent or in the molten state was sprayed 'by means of a nozzle on the moving pulverulent preparation.

The following Examples H1 to H7 describe the composition of some preparations according to the invention, which can be used as special products in the textile industry, in industrial laundries and, although to a lesser extent, in the home.

Percent (wt.) of constituents in the preparation according to Example- Constituents of the preparation H1 H2 H3 H4 H5 H6 H7 Perborate (mono) 22. 6 47. 1 Perborate (tetra) 50.0 36. 1 Activator 22.0 42.8 15.0 30.0 19.7 23.5 10.1 EDTA 2.2 2.0 0. DE'IPA- 4.8 0 ATMP- 1.6 N35P3010 34.6 42.2 23.1 15.2 9.8 N8zCO3 41.2 52.4 42.2 18.0 19.5 38.5 31.0

Percent (wt.) of constituents in the preparation according to Example- Constituents of the preparation W1 W2 W3 W4 W5 O 7.0 KA+9EO+12PO 2.0 6.6 Fs-ann'de 8 E0 3.5 Foam inhibitor 0. 6 0. 2 NasPaOm 35. 0 36. 5 38. 5 30. 1 NaaO-3.3 S10; 5.4 1.5 5.4 2.9 4. 5 NazSO4 0.3 0.5 3.4 3 6 5.0 N'IA Y 15. 0 EDTA 0 7 1.2 0. HEDP 14.0 .AIMP 1.1 CMC} 0.6 1.0 0.3 0.5 1.5 Mg 3 1.4 2.4 2.2 1.0 1.0 Perborate (mon 17.4 16.3 16.0 Perborate (tetra)- 4 25.0 Activator 11. 8 13. 7 9. O 17. 0 7. 0 Biii hikfif 0 5% 0 2 0 3 1 3 5 0 3 Remainder water Percent (wt,) of constituents in the preparation according to Example- Constituents of the preparation W6 W7 W8 W9 W10 ABS 6.0 Alknnnsulfnnnfn 2 9 HT-snlfnnntn KA-sulfate 1.5 TA-sulfate 0, 5 KA-EO-sulfate Soap C. OA+10 E0. KA+9EO+12 P Carboxybetairie. 0. Sulfobetaine 0.7 0.6 Foam inhibitor. 0.5 0.5 0.6 0.6 .0 36.4 41.1 38.0 .5 4.0 4.5 .0 2.5 0.8 .0 1.3 1.7 1.2

.0 6.0 3.0 12.0 .0 4.0 2.0 8.0 Brightener 0 0.35 0.25 029 Remainder water The bleaching liquors and baths, especially alkaline washing liquors prepared using the compositions according to the invention, show a better bleaching action than that obtained with known activators, both at treatment temperatures of, for example, 30" C. to 45 C., and at higher temperatures up to boiling. The higher degree of whiteness of the washed laundry is particularly noticeable when optical brighteners are simultaneously present.

This statement also applies in principal to working at lower temperatures of, for example, C. to 25 C., but a correspondingly longer time of treatment is necessary in this lower range of temperature.

If diacetyl-diketopiperazine is replaced by the dibenzoyl derivative, similar results are obtained.

The preceding specific embodiments are illustrative of the practice of the invention. It is apparent, however, that other expedients known to those skilled in the art or discussed herein, such as the use of the other named diacylated 2,5-diketopiperazines, may be employed without departing from the spirit of the invention.

We claim:

1. The method of activating aqueous solutions of percompounds selected from the group consisting of hydrogen peroxide and water-soluble peroxyhydrates containing from 5 mg. to 500 mg. per liter of active oxygen, said solution having a pH of from 7 to 13 and a temperature of from 10 C. to 70 C. which consists essentially of incorporating in said aqueous solution an activator diacylated 2,5-diketopiperazine having the formula wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbons selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, alkylbenzoic acid, nitroalkylbenzoic acid, haloalkylbenzoic acid, alkoxybenzoic acid and nitrilobenzoic acid, and R and R are members selected from the group consisting of hydrogen, alkyl having from. 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitriloalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms, said diacylated 2,5-diketopiperazine being incorporated in said aqueous solution in an amount suflicient that from 0.04 to 6 acyls in said diacylated 2,5-diketopiperazine are present per active oxygen atom in said aqueous solution.

2. The method of claim 1, wherein said aqueous solution has a pH of from 7.5 to 12.

3. The method of claim 2, wherein said aqueous solution has a pH of from 8 to 11.

4. The method of claim 1, wherein said diacylated 2,5- diketopiperazine is incorporated in said aqueous solution in an amount sufiicient that from 0.75 to 3 acyls in said diacylated 2,5-diketopiperazine are present per active oxygen atom in said aqueous solution.

5. The method of claim 1, wherein said activator diacylated 2,5-diketopiperazine is 1,4-diacetyl-2,5-diketopiperazine.

6. The method of claim 1, wherein said activator diacylated 2,5-diketopiperazine is l,4-dipropionyl-2,5-diketopiperazine.

7. The method of claim 1, wherein said activator diacylated 2,5-diketopiperazine is l,4-diacetyl-3,6-dimethyl- 1,5-diketopiperazine.

8. The method of claim 1, wherein said activator 2,5- diketopiperazine is 1,4-dibenzoyl-2,S-diketopiperazine.

9. The method of claim 1, wherein said aqueous solutions of said percompounds contain from 50 mg. to 250 mg. per liter of active oxygen.

10. Solid, powdery-to-granular oxidation compositions consisting essentially of from 10% to by weight of an activator diacylated 2,5-diketopiperazine having the formula wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbon atoms selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, alkylbenzoic acid, nitroalkylbenzoic acid, haloalkylbenzoic acid, alkoxybenzoic acid and nitrilobenzoic acid, and R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitriloalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms, and from 10% to 90% by weight of at least one alkaline-reacting builder salt.

11. The composition of claim 10, wherein said activator is present in an amount of from 20% to 70% by weight.

12. The composition of claim 10, wherein said activator diacylated 2,5-diketopiperazine is 1,4-diacetyl-2,5-diketopiperazine.

13. The composition of claim 10, wherein said activator diacylated 2,5-diketopiperazine is 1,4-dipropionyl-2,5-diketopiperazine.

14. The composition of claim 10, wherein said activator diacylated 2,5-diketopiperazine is l,4-diacetyl-3,6-dimethyl-2,S-diketopiperazine.

15. The composition of claim 10, wherein said activator 2,5-diketopiperazine is 1,4-dibenzoyl-2,S-diketopiperazine.

16. Solid, powdery-to-granular oxidation compositions consisting essentially of a water-soluble solid inorganic per-compound in the form of its alkali metal salt and a diacylated 2,5-diketopiperazine activator having the formula wherein R and R are acyls of organic carboxylic acids having from 2 to 9 carbon atoms selected from the group consisting of alkanoic acids, nitriloacetic acid, haloalkanoic acids, benzoic acid, nitrobenzoic acid, halobenzoic acid, alkylbenzoic acid, nitroalkylbenzoic acid, haloalkylbenzoic acid, alkoxybenzoic acid and nitrilobenzoic acid, and R and R are members selected from the group consisting of hydrogen, alkyl having from 1 to 3 carbon atoms, hydroxyalkyl having 1 to 3 carbon atoms, haloalkyl having 1 to 3 carbon atoms, nitroalkyl having 1 to 3 carbon atoms, nitriloalkyl having 2 to 4 carbon atoms and alkoxyalkyl having 2 to 5 carbon atoms, said diacylated 2,5-diketopiperazine being present in an amount sufr'icient that from 0.04 to 6 acyls in said diacylated 2,5- diketopiperazine are present per active oxygen atom in said per-compound.

17. The solid, powdery to granular oxidation compositions of claim 16, wherein said diacylated 2,5-diketopiperazine is present in an amount sufiicient that from 0.75 to 3 acyls in said diacylated 2,5-diketopiperazine are present per active oxygen atom in said per-compound.

tions of claim 16, wherein said activator diacylated 2,5-.

diketopiperazine is 1,4-dipropionyl-Z,S-diketopiperazine.

22. A method of bleaching textiles at temperatures below C. which comprises treating said textiles with an aqueous solution of the said solid oxidation compositions of claim 16 at a temperature below 70 C. and above 20 C.

References Cited UNITED STATES PATENTS 2,750,383 6/1956 Safir et a1. 260-268 DK 3,142,530 7/1964 Kokorutz 260-268 DKX 3,539,572 11/1970 Schroder et a1 8-107 X MAYER WEINBLATT, Primary Examiner US. Cl. X.R. 

